JP6269837B2 - リチウム二次電池 - Google Patents
リチウム二次電池 Download PDFInfo
- Publication number
- JP6269837B2 JP6269837B2 JP2016536056A JP2016536056A JP6269837B2 JP 6269837 B2 JP6269837 B2 JP 6269837B2 JP 2016536056 A JP2016536056 A JP 2016536056A JP 2016536056 A JP2016536056 A JP 2016536056A JP 6269837 B2 JP6269837 B2 JP 6269837B2
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- Japan
- Prior art keywords
- negative electrode
- active material
- electrode active
- secondary battery
- lithium secondary
- Prior art date
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 70
- 229910052744 lithium Inorganic materials 0.000 title claims description 70
- 208000028659 discharge Diseases 0.000 claims description 136
- 239000007773 negative electrode material Substances 0.000 claims description 128
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000010439 graphite Substances 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007774 positive electrode material Substances 0.000 claims description 11
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- 238000004519 manufacturing process Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000011149 active material Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
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- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
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Description
本出願は、2014年6月26日付韓国特許出願第2014-0079097号及び2015年6月19日付韓国特許出願第2015-0087199号に基づいた優先権の利益を主張し、当該韓国特許出願の文献に開示されている全ての内容は、本明細書の一部として含まれる。
本発明はリチウム二次電池に関し、より詳しくは、負極の初期充放電効率が正極の初期充放電効率より低いリチウム二次電池に関する。
<負極の初期充放電効率が84.7%で、正極の初期充放電効率が93%であるリチウム二次電池の製造>
第1負極活物質として初期充放電効率が約93%で、平均粒径が約15μmである黒鉛、及び第2負極活物質として初期充放電効率が約5%で、平均直径が約2μmであるSi粉末を99:1の重量比で混合して混合負極活物質を製造した。
正極活物質としてLi(Ni0.8Mn0.1Co0.1)O2、導電材としてsuper-p、及びバインダーとしてポリビニリデンフルオリドを95:2.5:2.5で混合して得た正極活物質スラリーを製造した。製造されたスラリーをアルミニウム集電体の片面にコーティングし、乾燥及び圧延した後、一定の大きさにパンチングして正極を製造した。
エチレンカーボネート(EC):プロピレンカーボネート(PC): ジエチルカーボネート(DEC)= 3:2:5(体積比)の組成を有する有機溶媒及び1.0MのLiPF6を添加して非水性電解液を製造した。
<負極の初期充放電効率が87.1%で、正極の初期充放電効率が88%であるリチウム二次電池の製造>
<負極の初期充放電効率が82%で、正極の初期充放電効率が93%であるリチウム二次電池の製造>
<負極の初期充放電効率が93%で、正極の初期充放電効率が93%であるリチウム二次電池の製造>
<負極の初期充放電効率が93%で、正極の初期充放電効率が88%であるリチウム二次電池の製造>
前記実施例1から3、及び比較例1、2で製造された正極及び負極をそれぞれ 0.1Cの定電流(CC)で5mVになるまで充電し、以後、定電圧(CV)で充電して充電電流が0.005Cになるまで1回目の充電を行った。以後、30分間放置した後、0.1Cの定電流で1.5Vになるまで放電して1回目の放電容量を測定した。このとき、1回目の充電容量と放電容量から初期充放電効率を計算した。その結果を下記表1に示した。
本発明に係るリチウム二次電池において、正極及び負極における初期充放電効率の制御に伴う抵抗特性改善の効果を評価した。
Claims (19)
- 負極及び正極を含むリチウム二次電池であって、
前記負極は、炭素系物質からなる第1負極活物質、及び前記第1負極活物質より初期充放電効率が低い第2負極活物質を含み、
前記負極の初期充放電効率は、正極の初期充放電効率より低く、
前記負極の初期充放電効率は、正極の初期充放電効率より0.5%超過から9%以下の範囲で低く、
前記正極は、正極活物質としてLi(Ni a Co b Mn c )O 2 (ここで、0<a<1、0<b<1、0<c<0.5、a+b+c=1)及びLi(Ni a Co b Al c )O 2 (ここで、0<a<1、0<b<1、0<c<1、a+b+c=1)及びこれらの混合物からなる群より選択されるいずれか一つを含むものである
リチウム二次電池。 - 前記負極の初期充放電効率は、80%から92%である請求項1に記載のリチウム二次電池。
- 前記負極の非可逆容量は、正極の非可逆容量よりさらに大きいものである請求項1または2に記載のリチウム二次電池。
- 前記第1負極活物質は、黒鉛である請求項1から3のいずれか一項に記載のリチウム二次電池。
- 前記第1負極活物質の平均粒径(D50)は、2μmから30μmである請求項1から4のいずれか一項に記載のリチウム二次電池。
- 前記第2負極活物質は、第1負極活物質より初期充放電効率が20%から90%さらに低いものである請求項1から5のいずれか一項に記載のリチウム二次電池。
- 前記第2負極活物質は、Si系、Sn系及びこれらの酸化物からなる群より選択されるいずれか一つ、またはこれらのうち1種以上の混合物を含むものである請求項1から6のいずれか一項に記載のリチウム二次電池。
- 前記第2負極活物質は、Si及びSiOx(ここで、xは0<x<2)からなる群より選択されるいずれか一つ、またはこれらのうち1種以上の混合物を含むものである請求項7に記載のリチウム二次電池。
- 前記第2負極活物質の平均粒径(D50)は、50nmから10μmである請求項1から8のいずれか一項に記載のリチウム二次電池。
- 前記第2負極活物質は、二次電池の初期充放電段階でばかり反応に参加するものである請求項1から9のいずれか一項に記載のリチウム二次電池。
- 前記第1負極活物質と第2負極活物質の混合比は、80:20から99.95:0.05重量比の範囲である請求項1から10のいずれか一項に記載のリチウム二次電池。
- 前記負極は、第1負極活物質として平均直径(D50)が2μmから30μmである黒鉛を含み、そして前記第2負極活物質として平均直径(D50)が50nmから10μmである、Si及びSiOx(ここで、xは0<x<2)からなる群より選択されるいずれか一つまたは二以上の混合物を含むものである請求項1から11のいずれか一項に記載のリチウム二次電池。
- 前記負極は、第1負極活物質として黒鉛を含み、前記第2負極活物質としてSi及びSiOx(ここで、xは0<x<2)からなる群より選択されるいずれか一つまたは二以上の混合物を含み、前記第1負極活物質と第2負極活物質の混合比は80:20から99.95:0.05重量比の範囲である請求項1から11のいずれか一項に記載のリチウム二次電池。
- 前記負極は、第1負極活物質として平均直径(D50)が2μmから30μmである黒鉛を含み、前記第2負極活物質として平均直径(D50)が50nmから10μmである、Si及びSiOx(ここで、xは0<x<2)からなる群より選択されるいずれか一つまたは二以上の混合物を含み、前記第1負極活物質と第2負極活物質の混合比は80:20から99.95:0.05重量比の範囲である請求項1から11のいずれか一項に記載のリチウム二次電池。
- 前記第1負極活物質上に第2負極活物質がコーティングされるか、前記第2負極活物質上に第1負極活物質がコーティングされてなる請求項1から11のいずれか一項に記載のリチウム二次電池。
- 前記第1負極活物質及び第2負極活物質は混合されるか、互いに複合化されて複合体として含まれる請求項1から11のいずれか一項に記載のリチウム二次電池。
- 前記負極は、前記第1負極活物質より初期充放電効率がさらに高い第3負極活物質をさらに含むものである請求項1から16のいずれか一項に記載のリチウム二次電池。
- 前記負極の初期放電は、1.5V以下まで行われるものである請求項1から17のいずれか一項に記載のリチウム二次電池。
- 前記負極は、第1負極活物質として黒鉛を含み、第2負極活物質としてSi系またはその酸化物を含むものである請求項1から11のいずれか一項に記載のリチウム二次電池。
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US20160197340A1 (en) | 2016-07-07 |
KR101697008B1 (ko) | 2017-01-16 |
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